Stream Dissolved Organic Matter Research Articles

Composition of Stream Dissolved Organic Matter Across Canadian Forested Ecozones Varies in Three Dimensions Linked to Landscape and Climate

AbstractDissolved organic matter (DOM) is a key variable influencing aquatic ecosystem processes. The concentration and composition of DOM in streams depend on both the delivery of DOM from terrestrial sources and on aquatic DOM production and degradation. However, there is limited understanding of the variability of stream DOM composition at continental scales and the influence of landscape characteristics and disturbances on DOM across different regions. We assessed DOM composition in 52 streams at seven research sites across six forested ecozones in Canada in 2019–2022 using 26 indices derived from five analytical approaches: absorbance and fluorescence spectroscopy, liquid chromatography—organic carbon detection, Fourier‐transform ion cyclotron resonance mass spectrometry, and asymmetric flow field‐flow fractionation. Combined analyses showed clear clustering and redundancy across analytical techniques, and indicated that compositional variations were primarily related to three axes of DOM composition: (a) aromaticity, which was greater in low‐relief, wetland‐dominated catchments, (b) oxygenation, which was greater in colder and drier ecozones, and (c) biopolymer content, which was greater in lake‐influenced catchments. Variability in DOM composition among research sites was greater than variability of streams within a site and variability over time within a stream. Forest harvesting and wildfire disturbances had no common influence on DOM composition across research sites, emphasizing the need for regional studies. Our study provides a broad understanding of the variability of stream DOM composition and its associations with landscape and catchment characteristics at a subcontinental scale, and provides key insights for the choice and interpretation of DOM indices from various analytical approaches.

Effects of reservoir construction on optical and molecular characteristics of dissolved organic matter in a typical P-contaminated river

The source and composition characteristics of dissolved organic matter (DOM) are crucial to identify and evaluate the sources of pollution in the watershed. The construction of reservoirs changes the hydrological condition and pollutant fate of the river. However, the effects of reservoirs' construction on DOM in the watershed and the underlying mechanisms are still unclear. This study aims to examine and compare the characteristics of DOM in reservoirs and streams in the Huangbai River, a typical reservoir-affected and P-contaminated river within the Yangtze River catchment. The results showed that DOM in reservoirs was characterized by more contribution from autochthonous source, under the influence of reservoirs’ construction; while, DOM in rivers was mainly originated from terrestrial input. Reservoirs had more lipid-like and protein-like compounds, while rivers contained more oxy-aromatic-like compounds. The percentage of CHOP molecules in reservoirs was significantly higher than that in rivers. The underlying mechanism is that more suitable conditions were created for plankton to grow after constructing reservoirs, which converted inorganic orthophosphate into organic phosphorus, and over time, organic phosphorus was gradually enriched in reservoirs, which exacerbated the risk of eutrophication in the reservoir water body. This study can provide theoretical support for monitoring and evaluation of water quality in reservoir-affected rivers.

Seasonal Trends of DOM Character in Soils and Stream Change With Snowmelt Timing

AbstractIn many watersheds, runoff occurring with snowmelt brings the largest pulse of dissolved organic matter (DOM) from soils to streams. Yet, exactly how soil and stream DOM fractions are altered as snowmelt timing changes is not well understood. We studied the optical character of DOM as it moved through a first‐order northern hardwood watershed through the snowmelt period. While stream dissolved organic carbon (DOC; mean = 4.6 mg C L−1) concentrations were not correlated with snowmelt flushing, stream DOM appeared humic‐like throughout the study period (humification index, HIX; mean = 10.9). Within the stream, we measured seasonal increases in an inverse index of DOM molecular weight and processing (spectral slope, S275–295; range = 0.0102–0.0214) and in an index of recently derived DOM (Biological Index, BIX; range = 0.2–1.1). We measured a decrease in an inverse index of DOM oxidation (ratio of Peak C to Peak A, or C/A; range = 0.59–2.01) through the snowmelt period. Stream BIX and C/A tracked those measured in the north aspect soils throughout the study. C/A was unique as it decreased from source to stream, likely reflecting the diagenesis of DOM through soils. These data suggest that changes in the timing of snowmelt and hydrologic connectedness within a watershed affect seasonal changes in stream DOM character. We suggest that watersheds with deep glacial till parent materials have stream connectivity limited by subsurface flow paths, with stream DOM character being determined largely by slow melt and a longer period of infiltration.

Groundwater Plays an Important Role in Controlling Riverine Dissolved Organic Matter in a Cold Alpine Catchment, the Qinghai–Tibet Plateau

AbstractIn cold alpine areas, the hydrological control on dissolved organic matter (DOM) export in relation to permafrost distribution remains uncertain on a catchment scale. To address this, the seasonal variations in DOM chemical features of groundwater and stream water were examined from 2013 to 2019 in a representative catchment on the northeastern Qinghai–Tibet Plateau, which is covered by both permafrost (at elevations higher than 3,500 m a.s.l.) and seasonally frozen areas. The results show that the highest dissolved organic carbon (DOC) concentration occurred during the thawing period (April–May), while the highest DOC flux occurred during the thawed period (June–early October). In the permafrost area, the freeze–thaw process significantly influenced the groundwater flow paths and DOM. During the thawing period, with shallow groundwater flow path through the organic soil layer, the stream water DOM recharged by suprapermafrost groundwater was characterized by high aromaticity and high DOC concentrations. During the thawed period, the deepening groundwater flow path through the mineral layer and dilution by overland flow, resulted in low DOC concentrations and DOM with lower aromaticity in stream water. When groundwater flowed from the permafrost area into the porous aquifers in the seasonally frozen area, the groundwater flow path also affected DOM dynamics. The stream water at the catchment outlet, which received groundwater discharge from the porous aquifer, showed a lower peak DOC concentration, a higher proportion of protein‐like DOM, and a higher contribution of cold season DOC flux to annual DOC flux when compared to the water flowing out from the permafrost area. Our work highlights the role of the thick, porous aquifer in the seasonally frozen area in regulating DOM export. The results suggest that the cold alpine area may exhibit a stronger positive feedback to climate warming than that in Arctic areas.

Bioavailability of dissolved organic matter varies with anthropogenic landcover in the Upper Mississippi River Basin

Anthropogenic conversion of forests and wetlands to agricultural and urban landcovers impacts dissolved organic matter (DOM) within streams draining these catchments. Research on how landcover conversion impacts DOM molecular level composition and bioavailability, however, is lacking. In the Upper Mississippi River Basin (UMRB), water from low-order streams and rivers draining one of three dominant landcovers (forest, agriculture, urban) was incubated for 28 days to determine bioavailable DOC (BDOC) concentrations and changes in DOM composition. The BDOC concentration averaged 0.49 ± 0.30 mg L−1 across all samples and was significantly higher in streams draining urban catchments (0.72 ± 0.34 mg L−1) compared to streams draining agricultural (0.28 ± 0.15 mg L−1) and forested (0.47 ± 0.17 mg L−1) catchments. Percent BDOC was significantly greater in urban (10% ± 4.4%) streams compared to forested streams (5.6% ± 3.2%), corresponding with greater relative abundances of aliphatic and N-containing aliphatic compounds in urban streams. Aliphatic compound relative abundance decreased across all landcovers during the bioincubation (average -4.1% ± 10%), whereas polyphenolics and condensed aromatics increased in relative abundance across all landcovers (average of +1.4% ± 5.9% and +1.8% ± 10%, respectively). Overall, the conversion of forested to urban landcover had a larger impact on stream DOM bioavailability in the UMRB compared to conversion to agricultural landcover. Future research examining the impacts of anthropogenic landcover conversion on stream DOM composition and bioavailability needs to be expanded to a range of spatial scales and to different ecotones, especially with continued landcover alterations.

Different dissolved organic matter composition between central and southern glaciers on the Tibetan Plateau

A large amount of dissolved organic matter (DOM) is stored in glacier ecosystems, which is crucial for downstream oligotrophic aquatic ecosystems during glacier melting. However, knowledge about their spatial differences in glacier ecosystems on the Tibetan Plateau (TP) is limited. We qualitatively and quantitatively analyzed the DOM in snow, ice, cryoconite, and glacier-fed streams in five glaciers in the central and southern TP using ultra-high-resolution mass spectrometry. Our results revealed that there were no significant differences in DOM concentrations or composition between the central and southern TP glaciers in snow and ice samples. However, the southern cryoconite contained significantly higher relative intensities of carbohydrate-, lignin-, tannin-, and condensed aromatic-like compounds and lower intensities of lipid-like compounds than the central cryoconite. In addition, the DOM molecules sustained in the cryoconite of the southern glacier were predominantly classified as condensed aromatic-like compounds, whereas those of the central TP glaciers were classified as lignin-like compounds. Except different terrestrial input, the network analysis and backward trajectory revealed that different bacterial composition and anthropogenic inputs caused this difference. Higher forest cover leaded to higher relative intensities of lignin- and tannin- DOM in the southern cryoconite than the central cryoconite. Sixty-six operational taxonomic units (OTUs) were associated with the degradation of lipid-, proteins/amino sugar- and lignin-like components which showed significantly higher relative abundance in the southern cryoconite than the central cryoconite. More anthropogenic inputs brought by the India monsoon affect the carbohydrate- and condensed aromatic-like compounds in the southern cryoconite. DOM exported into glacial streams of the central TP glaciers was dominated by tannin- and condensed aromatic-like compounds, whereas more labile components were discharged from the southern TP glacier. Our study provides new insights on the glacier DOM composition in and exported from different glaciers in the face of changing climate.

Factors Controlling the Spatial Distribution of Dissolved Organic Matter With Changes in the C/N Ratio From the Upper to Lower Reaches of the Ishikari River, Japan

Dissolved organic matter (DOM), particularly dissolved organic nitrogen (DON), is an important source of energy and/or organic nutrients for heterotrophic microorganisms in rivers. Although various factors controlling the quantity and quality of stream and riverine DOM have been extensively studied, DON has been under-researched compared to dissolved organic carbon (DOC). The spatial distribution of DOC and DON concentrations with respect to the C/N ratio and DOM optical properties was investigated in the Ishikari River and its tributaries in Hokkaido, northern Japan. Here, the upper reaches are forested and the middle and lower reaches are encompassed by agricultural land, in particular paddy fields. Furthermore, dark incubation experiments were conducted using filtered riverine water (<0.7 µm) to determine the bioavailability of DOC and DON (particularly due to small microorganisms) considered as a factor controlling the spatial distribution. In the mainstream, DOC and DON concentrations increased with river flow in the upper and middle reaches and remained unchanged in the lower reaches. The C/N ratio of bulk DOM decreased continuously from the upper reaches to lower reaches. The optical properties exhibited changes in the DOM characteristics in terms of higher molecular weight and higher aromaticity from the upper to middle reaches, suggesting that flooded paddy fields largely altered the riverine DOM concentration and composition. In the lower reaches, the C/N ratio of the bulk DOM decreased with the river flow. However, according to principal component analysis, no changes were observed in the optical properties with river flow, suggesting that the C/N ratio of bulk DOM changed owing to in situ biological activity in the river. DOC biodegradation was observed at four sites in the upper and middle reaches but not at the two sites in the lower reaches. However, the DON concentration during the dark incubation experiments at all sites did not differ significantly, which implies that microbial degradation, particularly by small microorganisms, is a factor that decreased the C/N ratio of bulk DOM in the upper and middle reaches. In contrast, large microorganisms possibly degraded C-rich DOM to decrease the C/N ratio of bulk DOM in the lower reaches of the Ishikari River.

Land Use Overrides Stream Order and Season in Driving Dissolved Organic Matter Dynamics Throughout the Year in a River Network.

Anthropogenic land use has increased nutrient concentrations and altered dissolved organic matter (DOM) character and its bioavailability. Despite widespread recognition that DOM character and its reactivity can vary temporally, the relative influence of land use and stream order on DOM characteristics is poorly understood across seasons and the entire flow regime. We examined DOM character and 28-day bioavailable dissolved organic carbon (BDOC) across a river network to determine the relative roles of land use and stream order in driving variability in DOM character and bioavailability throughout the year. DOM in 1st-order streams was distinct from higher stream orders with lower DOC concentrations, less aromatic (specific ultraviolet absorbance at 254 nm (SUVA254)), more autochthonous (fluorescence index), and more recently produced (β/α) DOM. Across all months, variability in DOM character was primarily explained by land use, rather than stream order or season. Land use and stream order explained the most DOM variation in transitional and winter months and the least during dry months. BDOC was greater in watersheds with less aromatic (SUVA254) and more recent allochthonous DOM (β/α) and more development and impervious surface. With continued development, the bioavailability of DOM in the smallest and most impacted watersheds is expected to increase.

Enhanced chemodiversity, distinctive molecular signature and diurnal dynamics of dissolved organic matter in streams of two headwater catchments, Southeastern China

Dissolved organic matter (DOM) is a complicated assembly of organic molecules, including thousands of molecules with various structures and properties. However, how the stream DOM sources respond to carbon compositions and the transformation processes remains unclear. In this study, the chemical characteristics and spectral and mass spectrometry (FT-ICR MS) of DOM were analyzed. Six sampling points of headwater stream (HWSs) were sampled, and an effluent polluted stream (WSR) and a main stream of the Changjiang River (DT) were also sampled for comparison. In situ degradation experiments and FT-ICR MS analysis were also performed to observe the dynamic processes of DOM in HWS. The results showed that the anthropogenic markers of sewage (i.e. sulfur (S) compounds and marker from antibiotics and estrogen) in HWS were higher than those in DT. The molecular weight decreased while the degradation products (S-containing compounds and unsaturated compounds (HU)) increased after in situ degradation due to the influence of both the photodegradation and biodegradation process. In addition, the KMD plots showed that the DOM homologue intensities in range 400–600 Da changed significantly after demethylation by biodegradation. The components of highly refractory substances and the degradation degree of DOM in DT was higher than that in HWS. We extracted the refractory DOM pool in HWS, which was mainly small molecular with molecular weights < 600 Da. These molecular will be difficult to remove in traditional drinking water treatment processes and easily produced disinfection byproducts (DBPs). This study emphasized the necessity of identifying the sources and transformation processes of DOM in HWS and clarified the types and characteristics of DOM that should be considered in future drinking water treatment.

Hydrological seasonality and nutrient stoichiometry control dissolved organic matter characterization in a headwater stream

Dissolved organic matter (DOM) is a diverse and highly complex mixture of organic macromolecules, and thus plays a central role in aquatic ecosystems. However, responses of components and sources of DOM to hydrological processes and trophic levels (nutrient stoichiometric ratios) are poorly understood, particularly in monsoonal headwater streams of Asia that are vulnerable to catchment physical characteristics. In this study, the excitation - emission matrix florescence spectroscopy coupled with parallel factor analysis (EEM-PARAFAC) was used to explore the DOM characters in a headwater stream, where seasonal rainfalls and nutrient levels vary largely. The EEM-PARAFAC modelling identified one autochthonous protein-like fluorescence substance (C1) and two allochthonous fulvic- and humic-like fluorescence compounds (C2 and C3). The allochthonous compounds dominated the overall DOM signal in the headwaters. The hydrological seasonality coupled with nutrients was key in modulating headwater DOM sources and components. Seasonal rainfall events contributed more allochthonous terrestrial-derived DOM flushing into river waters, resulting in higher fulvic- and humic-like organic matter (C2 + C3) in the wet season. In the dry season, longer water residence time accompanying with higher C:P stoichiometric ratio was responsible for higher autochthonous microbial- and plant-derived DOM (tryptophan and tyrosine fractions), also reflected by higher C1, biological index (BIX) and freshness index (β:α). In-stream microbial metabolism of labile DOM fractions largely contributed to autochthonous DOM and partial pressure CO2 increase in the headwater stream. Our findings indicate that quality and quantity of DOM in headwater streams play a crucial role in downstream carbon cycle. Furthermore, the evidence combined from PARAFAC components, pCO2 and spectral slope clearly highlights the importance of microbial metabolism of carbon in lotic systems, especially during a dry season with increased residence time.

Conditioning Film and Early Biofilm Succession on Plastic Surfaces.

In the context of environmental plastic pollution, it is still under debate if and how the "plastisphere", a plastic-specific microbial community, emerges. In this study, we tested the hypothesis that the first conditioning film of dissolved organic matter (DOM) sorbs selectively to polymer substrates and that microbial attachment is governed in a substrate-dependent manner. We investigated the adsorption of stream water-derived DOM to polyethylene terephthalate (PET), polystyrene (PS), and glass (as control) including UV-weathered surfaces by Fourier-transform ion cyclotron mass spectrometry. Generally, the saturated, high-molecular mass and thus more hydrophobic fraction of the original stream water DOM preferentially adsorbed to the substrates. The UV-weathered polymers adsorbed more polar, hydrophilic OM as compared to the dark controls. The amplicon sequencing data of the initial microbial colonization process revealed a tendency of substrate specificity for biofilm attachment after 24 h and a clear convergence of the communities after 72 h of incubation. Conclusively, the adsorbed OM layer developed depending on the materials' surface properties and increased the water contact angles, indicating higher surface hydrophobicity as compared to pristine surfaces. This study improves our understanding of molecular and biological interactions at the polymer/water interface that are relevant to understand the ecological impact of plastic pollution on a community level.

Agricultural land use changes stream dissolved organic matter via altering soil inputs to streams

Agricultural land use leads to significant changes in both the quality (e.g., sources and compositions) and quantity of dissolved organic matter (DOM) exported from terrestrial to aquatic ecosystems. However, the effect of agricultural activities often interacts with those of hydroclimatic drivers, making it difficult to delineate agriculture-induced changes and identify associated mechanisms. Using partial least square path modeling (PLS-PM), we examined the relative importance of agricultural land use, stream order, precipitation, and temperature in mediating allochthonous versus autochthonous sources and pathways that influenced stream DOM quality and quantity. We analyzed stream water DOM from 15 small streams draining watersheds across a gradient of agricultural land use in Southeast USA for about one year. For DOM quantity, agricultural land use increased the export of DOC and various DOM pools (terrestrial humic, microbial humic, and protein-like DOM) from land to streams, and for DOM quality, agricultural streams showed greater proportions of microbial humic compounds than forested streams. The PLS-PM model for DOM quantity accounted for 75.5% of total variance and identified that agricultural land use increased stream water DOM quantity primarily through increasing allochthonous inputs, which can be attributed to shallower flow paths in agricultural watersheds that enabled the export of organic materials from the upper, organic-rich soil horizon. PLS-PM models for DOM quality only explained ~13% of the total variance, highlighting the complex dynamics between environmental drivers and stream water DOM. Relative to commonly used multivariate statistic modeling (e.g., redundancy analysis (RDA)), PLS-PM models offer the advantages of identifying the primary pathway by which agricultural lands alter freshwater DOM and quantifying the relative importance of interactive effects of agriculture and hydroclimatic drivers. Therefore, structural equation modeling is a powerful tool that should be more widely adopted to distinguish among multiple drivers and mechanisms regulating freshwater biogeochemistry.

Dissolved Organic Matter Processing in Pristine Antarctic Streams.

Accelerated glacier melt and runoff may lead to inputs of labile dissolved organic matter (DOM) to downstream ecosystems and stimulate the associated biogeochemical processes. However, still little is known about glacial DOM composition and its downstream processing before entering the ocean, although the function of DOM in food webs and ecosystems largely depends on its composition. Here, we employ a set of molecular and optical techniques (UV-vis absorption and fluorescence spectroscopy, 1H NMR, and ultrahigh-resolution mass spectrometry) to elucidate the composition of DOM in Antarctic glacial streams and its downstream change. Glacial DOM consisted largely of a mixture of small microbial-derived biomolecules. 1H NMR analysis of bulk water revealed that these small molecules were processed downstream into more complex, structurally unrecognizable molecules. The extent of processing varied between streams. By applying multivariate statistical (compositional data) analysis of the DOM molecular data, we identified molecular compounds that were tightly associated and moved in parallel in the glacial streams. Lakes in the middle of the flow paths enhanced water residence time and allowed for both more DOM processing and production. In conclusion, downstream processing of glacial DOM is substantial in Antarctica and affects the amounts of biologically labile substrates that enter the ocean.

Stream Macroinvertebrates and Carbon Cycling in Tangled Food Webs

The annual global loss of organic carbon from terrestrial ecosystems into rivers is similar to the organic carbon stored in soils each year. Dissolved organic matter (DOM) flows through the food web to macroinvertebrates, but little is known about the effect of DOM increase on stream food webs and how much macroinvertebrates may contribute to the regulation of carbon fluxes in rivers. Using a before and after control impact (BACI) experimental design, we increased by 12% (+ 0.52 mg C L−1) the concentration of DOM in a stream for three weeks by adding sucrose, with a distinctive δ13C signature, to simulate a pulse of natural DOM supply from soils. We partitioned the diet of macroinvertebrates from carbon sources according to the green pathway (autotrophs) and detrital pathways (bacteria and terrestrial organic matter). Our flow food web approach based on C fluxes, with bacteria as a key node, showed the dominant contribution of the detrital pathways for macroinvertebrates in the reference stream. DOM addition induced changes in the diets of individual taxa, but did not have any strong effects on the relative overall contribution of the detrital pathways versus the green pathway. Autotrophic uptake of CO2 respired by bacteria was much larger than bacterial C flux to invertebrates (that is, the classic microbial loop) and allowed a significant fraction of natural allochthonous organic carbon to make its way to macroinvertebrates via autotrophs fixing CO2 respired by bacteria. Overall macroinvertebrates did not regulate directly to any great extent the flux of stream DOM towards downstream ecosystems.

Optical properties and 14C ages of stream DOM from agricultural and forest watersheds during storms.

Forest and agricultural land use affects the concentration and composition of dissolved organic carbon (DOC) in streams and rivers. To elucidate the impacts of forest and agricultural land use on stream DOC during storm events, we investigated DOC concentration ([DOC]), optical properties of dissolved organic matter (DOM), and Δ14C-DOC in both forest- and agriculture-dominated headwater streams in South Korea in the summer of 2012. One forested and five agricultural streams were investigated. During storms, the peak [DOC] of forest stream increased to 5.8mgL-1, approximately two times larger than that of the most agricultural stream (3.2mgL-1), demonstrating the weaker storm responses of the [DOC] of agricultural streams to hydrological change. Five PARAFAC components were identified, including three terrestrial humic-like substances (C1, C2, C3), one microbial humic substance (C4), and one microbial protein-like substances (C5). The mean (C4+C5)/(C1+C2+C3) of all storm events at the most agricultural stream was 1.5 times larger than that of the most forested stream, suggesting that more protein-like DOM is exported from agricultural watersheds. Whereas a forest stream was primarily composed of terrestrially derived and 14C-enriched modern DOC, the 14C-age of the most agricultural stream was up to ∼1000 years old. The results suggest that agricultural practices could decrease the old organic carbon pools from soils. However, how quickly the aged DOC can be degraded to CO2 in streams is unknown, warranting future investigation on lability of the aged DOC and their effects on CO2 evasion from rivers and estuaries downstream.

Stormflows Drive Stream Carbon Concentration, Speciation, and Dissolved Organic Matter Composition in Coastal Temperate Rainforest Watersheds

AbstractStream water carbon concentrations can be highly dynamic on the time scales of both individual storm events and seasonal hydroclimatic shifts. We collected stream water daily over a 6‐day storm from three headwater subcatchments of varying landcover (poor fen, forested wetland, and upland forest) and the catchment outlet to evaluate how precipitation events impact the concentration and speciation of carbon (organic vs. inorganic) as well as the composition of dissolved organic matter (DOM) exported laterally from coastal temperate rainforest catchments. Dissolved and particulate organic carbon concentrations increased during the storm at all sites, while dissolved inorganic carbon concentrations were diluted during peak flows. These results highlight the importance of quantifying all forms of lateral carbon export when evaluating the role of storms in catchment‐scale carbon cycling. Isotopic hydrograph separation using stream water δ18O showed that percent new water was significantly related to carbon concentration and form providing a clear link between stream water sources (i.e., recent event water) and soil carbon source areas that become connected to surface water during storms. Furthermore, ultrahigh‐resolution mass spectrometry showed that stream water DOM exported from the upland forest contained the greatest molecular diversity of the three landscape types and had the largest changes in composition over the storm suggesting that the wetland‐dominated subcatchments were less compositionally diverse with regard to soil DOM pools active during the storm. Overall, this study provides insight into hydro‐biogeochemical drivers that control lateral carbon export from forested catchments in a region where an increasing fraction of precipitation is falling as rain.

Landscape Influence on the Browning of a Lake Watershed in the Adirondack Region of New York, USA

Watershed recovery from long-term acidification in the northeastern U.S. has been characterized by an increase in the influx of dissolved organic matter (DOM) into surface waters. Increases in carbon quantity and shifts to more aromatic and “colored” OM has impacted downstream lakes by altering thermal stratification, nutrient cycling and food web dynamics. Here, we used fluorescence spectroscopy coupled with parallel factor analysis (PARAFAC) to model predominant carbon quality fractions and their seasonal changes within surface waters along landscape positions of Arbutus Lake watershed in the Adirondack region of NY, USA. All DOM components were terrestrial in origin, however their relative fractions varied throughout the watershed. DOM in headwater streams contained high fractions of recalcitrant (~43%) and microbial reprocessed humic-like OM (~33%), sourced from upland forest soils. Wetlands above the lake inlet contributed higher fractions of high molecular weight, plant-like organic matter (~30%), increasing dissolved organic carbon (DOC) concentrations observed at the lake inlet (492.5 mg L−1). At the lake outlet, these terrestrial fractions decreased significantly during summer months leading to a subsequent increase in reprocessed OM likely through increased microbial metabolism and photolysis. Comparisons of specific ultraviolet absorbance between this study and previous studies at Arbutus Lake show that OM draining upland streams (3.1 L·mg C−1 m−1) and wetland (4.1 L·mg C−1 m−1) is now more aromatic and thus more highly colored than conditions a decade ago. These findings provide insight into the emerging role that watersheds recovering from acidification play on downstream water quality.

Origin of dissolved organic matter in the Harz Mountains (Germany): A thermally assisted hydrolysis and methylation (THM-GC–MS) study

Environmental change is increasing the concentration of dissolved organic matter (DOM) in catchments of the Northern Hemisphere. This study aims to assess the causes of high DOM concentrations in streams and reservoirs of the Harz National Park (Germany), by means of molecular characterization using thermally assisted hydrolysis and methylation (THM-GC–MS). In order to formulate proxies of the prevailing origin of the numerous THM products of polyphenols, carbohydrates, proteins, aliphatic macromolecules, resins and other DOM precursors, we created a reference sample set of potential sources (spruce, birch, blueberry, heather, peat moss, soils) from the area. Besides solid-state reference samples (bulk organic matter; BOM) we obtained and analyzed their leachates (water-extractable OM; WEOM). Finally, an existing THM-GC–MS dataset of the DOM from the Oder river, which crosses the boundary between peat and forest biomes in the Harz, was extended and explored chemometrically using Principal Component Analysis (PCA) to test the proxies for stream DOM assessment. The results show large differences between BOM and WEOM, which suggests that the solid-to-leachate transition is highly selective or significantly alters the major biomolecular constituents. THM compounds that tend to be more abundant in WEOM than in BOM are G-type phenolic compounds (1,2-dimethoxybenzenes, from lignin and tannin), nitrogen-containing moieties and benzene carboxylic acids, whereas WEOM is depleted in products of polysaccharides, syringyl lignin and aliphatic macromolecules (cutin and suberin). The lignin fingerprint of the WEOM also differs significantly from that of BOM, being depleted in the vast majority of the typical products of macromolecular lignin (G7, G8, G14, G15) and enriched in the acid moiety (G6, predominantly from vanillic acid), especially for spruce wood. THM chromatograms of DOM from the forest section of the Oder show an extraordinary abundance of G6, most probably from spruce-derived lignin. This may indicate a major role of DOM released from decaying spruce logs and forest soils. The results highlight both the potential and the pitfalls associated with source identification of DOM using THM-GC–MS.

Wildfires lead to decreased carbon and increased nitrogen concentrations in upland arctic streams

The Central Siberian Plateau is undergoing rapid climate change that has resulted in increased frequency of forest fires and subsequent alteration of watershed carbon and nutrient dynamics. Across a watershed chronosequence (3 to >100 years since wildfire) we quantified the effects of fire on quantity and composition of dissolved organic matter (DOM), stream water nutrient concentrations, as well as in-stream nutrient uptake. Wildfires increased concentrations of nitrate for a decade, while decreasing concentrations of dissolved organic carbon and nitrogen (DOC and DON) and aliphatic DOM contribution for five decades. These post-wildfire changes in stream DOM result in lower uptake efficiency of in-stream nitrate in recently burned watersheds. Nitrate uptake (as uptake velocity) is strongly dependent on DOM composition (e.g. polyphenolics), ambient dissolved inorganic nitrogen (DIN), and DOC to DIN ratios. Our observations and experiments suggest that a decade-long pulse of inorganic nitrogen and a reduction of DOC export occur following wildfires in streams draining the Central Siberian Plateau. Increased fire frequency in the region is thus likely to both decrease DOM and increase nitrate delivery to the main stem Yenisei River, and ultimately the Arctic Ocean, in the coming decades.

Dynamics of dissolved organic matter in headwaters: comparison of headwater streams with contrasting DOM and nutrient composition

Dissolved organic matter (DOM) in freshwaters is recognised as a significant and active component of the global carbon budget. DOM exported from terrestrial ecosystems may be compositionally and functionally altered by chemical and biological reactions as it is transported downstream. The processes affecting DOM in headwater streams remain uncertain but are potentially highly variable depending on DOM composition and nutrient availability as a function of soils, land-use, and human pressures. To investigate variability of DOM reactivity we took water samples from two contrasting headwater catchments, considered functional ‘end-members’ for DOM export: one rich in aromatic DOM and low in inorganic nutrients (peatland), and another (nearby) catchment characterized by less aromatic DOM and high nutrient loadings (agricultural grassland). Under controlled laboratory conditions, we evaluated the effects of light, presence/absence of aquatic biota and nutrient enrichment on short-term changes in DOM quantity and quality in these samples. For the peat stream, exposure to sunlight (with UV) resulted in net abiotic DOM removal, whereas in the agricultural stream it led to net biological DOM production. Nutrient addition accelerated DOM production in both streams. We conclude that in-stream changes in DOM quantity and quality represent the net effect of multiple consumption and production processes whose relative importance is strongly influenced by source-dependent DOM composition and environmental factors such as inorganic nutrient content and sunlight exposure. Our findings suggest that headwater streams may be more active processors of carbon and nutrients than presumed hitherto.